13524-04-4Relevant articles and documents
Synthesis, Structure, Reactivity, and Catalytic Activity of Cyclometalated (Phosphine)- and (Phosphinite)ruthenium Complexes
Sun, Ruichen,Chu, Xiaodan,Zhang, Shaowei,Li, Tongyu,Wang, Zhuo,Zhu, Bolin
, p. 3174 - 3183 (2017)
Reactions of naphthyl- and o-methylphenyl-substituted phosphines with [RuCl2(p-cymene)]2 resulted in the corresponding phosphine-substituted ruthenium dichlorides (1a,b and 3). When the reactions of aryl-substituted phosphines or pho
Cyclometalated ruthenium(II) complexes as highly active transfer hydrogenation catalysts
Baratta, Walter,Da Ros, Paolo,Del Zotto, Alessandro,Sechi, Alessandra,Zangrando, Ennio,Rigo, Pierluigi
, p. 3584 - 3588 (2004)
Quantitative conversion: Reaction of the 14-electron complex [RuCl 2{(2,6-Me2C6H3)PPh2} 2] with CH2O in the presence of NEt3 gave a five-coordinate cyclometalated complex with a δ-agostic interaction of one ortho-methyl group (see X-ray crystal structure), Displacement of one phosphane group with 2-(amino-methyl)pyridine gave a highly active catalyst for the quantitative conversion of ketones into alcohols.
Uncatalyzed hydrogen-transfer reductions of aryl ketones
Srinivasan,Manisankar
, p. 1338 - 1347 (2011)
A simple, convenient, and environmentally benign procedure has been developed for exclusive reduction of aryl ketones by hydrogen transfer with sec-BuOH as hydrogen donor in the presence of KOH without supercritical conditions, ligands, and any catalytic utility.
Synthesis of 2-aminomethylpiperidine ruthenium(II) phosphine complexes and their applications in transfer hydrogenation of aryl ketones
Tuerkmen, Hayati
, p. 731 - 735 (2012)
The complex trans,cis-[RuCl2(PPh3)2(ampi)] (2) was prepared by reaction of RuCl2(PPh3)3 with 2-aminomethylpiperidine(ampi) (1). [RuCl2(PPh 2(CH2)nPPh2)(ampi) (n = 3, 4, 5)] (3-5) were synthesized by displacement of two PPh3 with chelating phosphine ligands. All complexes (2-5) were characterized by 1 H, 13C, 31P NMR, IR and UV-visible spectroscopy and elemental analysis. They were found to be efficient catalysts for transfer hydrogen reactions. Copyright
Enhancing cofactor regeneration of cyanobacteria for the light-powered synthesis of chiral alcohols
Fan, Jianhua,Zhang, Yinghui,Wu, Ping,Zhang, Xiaoyan,Bai, Yunpeng
, (2021/11/24)
Cyanobacteria Synechocystis sp. PCC 6803 was exploited as green cell factory for light-powered asymmetric synthesis of aromatic chiral alcohols. The effect of temperature, light, substrate and cell concentration on substrate conversions were investigated. Under the optimal condition, a series of chiral alcohols were synthesized with conversions up to 95% and enantiomer excess (ee) > 99%. We found that the addition of Na2S2O3 and Angeli's Salt increased the NADPH content by 20% and 25%, respectively. As a result, the time to reach 95% substrate conversion was shortened by 12 h, which demonstrated that the NADPH regeneration and hence the reaction rates can be regulated in cyanobacteria. This blue-green algae based biocatalysis showed its potential for chiral compounds production in future.
Highly Active Cooperative Lewis Acid—Ammonium Salt Catalyst for the Enantioselective Hydroboration of Ketones
Titze, Marvin,Heitk?mper, Juliane,Junge, Thorsten,K?stner, Johannes,Peters, René
supporting information, p. 5544 - 5553 (2021/02/05)
Enantiopure secondary alcohols are fundamental high-value synthetic building blocks. One of the most attractive ways to get access to this compound class is the catalytic hydroboration. We describe a new concept for this reaction type that allowed for exceptional catalytic turnover numbers (up to 15 400), which were increased by around 1.5–3 orders of magnitude compared to the most active catalysts previously reported. In our concept an aprotic ammonium halide moiety cooperates with an oxophilic Lewis acid within the same catalyst molecule. Control experiments reveal that both catalytic centers are essential for the observed activity. Kinetic, spectroscopic and computational studies show that the hydride transfer is rate limiting and proceeds via a concerted mechanism, in which hydride at Boron is continuously displaced by iodide, reminiscent to an SN2 reaction. The catalyst, which is accessible in high yields in few steps, was found to be stable during catalysis, readily recyclable and could be reused 10 times still efficiently working.
Selective C-alkylation Between Alcohols Catalyzed by N-Heterocyclic Carbene Molybdenum
Liu, Jiahao,Li, Weikang,Li, Yinwu,Liu, Yan,Ke, Zhuofeng
supporting information, p. 3124 - 3128 (2021/09/20)
The first implementation of a molybdenum complex with an easily accessible bis-N-heterocyclic carbene ligand to catalyze β-alkylation of secondary alcohols via borrowing-hydrogen (BH) strategy using alcohols as alkylating agents is reported. Remarkably high activity, excellent selectivity, and broad substrate scope compatibility with advantages of catalyst usage low to 0.5 mol%, a catalytic amount of NaOH as the base, and H2O as the by-product are demonstrated in this green and step-economical protocol. Mechanistic studies indicate a plausible outer-sphere mechanism in which the alcohol dehydrogenation is the rate-determining step.
